Catalysts for oxychlorination of ethylene to 1,2-dichlorethane comprising a copper compound, generally cupric chloride, and promoters based on salts of alkaline and/or alkaline-earth metals and rare earths are well-known in the literature.
The copper content of these catalysts generally is no more than 6-8% by weight.
Catalysts with a copper content that can reach 12-14% by weight are known from patent GB 1,189,815.
The catalysts are prepared by co-precipitation of a hydrogel of alumina and copper, followed by aging of the precipitate at 10°-40° C. for at least 10 hours, drying, and finally calcining at a temperature between 300 and 600° C. for a time sufficient to convert the alumina hydrogel into gamma alumina.
Differently from catalysts with a high copper content (12% by weight) obtained by impregnating alumina with a solution of a copper salt, which according to the patent cited above yield low conversions of hydrochloric acid and considerable combustion of the ethylene to carbon oxides, catalysts prepared by co-precipitation provide, again according to the patent, a good performance both in terms of conversion and selectivity and in terms of stability of the fluid bed.
However, these catalysts have the drawback that they require high spatial velocities and a consequent considerable recycling of the unconverted ethylene.
Catalysts with a high copper content (12-13% by weight) (probably prepared according to the co-precipitation method) are commercially available which have high activity but have the drawback of a considerable combustion of the ethylene even when working at relatively low temperatures (210° C.).
European patent application EP 1 464 395 describes catalysts for oxychlorination of ethylene which have a copper content of 7-12% by weight and comprise compounds of magnesium, prepared by impregnation of gamma alumina, which do not have the drawbacks of catalysts obtained by co-precipitation but provide a good performance both in terms of selectivity to 1,2-DCE and in terms of productivity.
The distribution of copper in these catalysts is such that the X/Y ratio, where X is the Al/Cu ratio at the surface, determined by XPS (X-ray Photoemission Spectroscopy) and Y is the Al/Cu ratio referred to the entire particle of catalyst, is comprised in the range between 0.8 and 1.3.
The examples of the European application show that as the X/Y ratio rises from 0.91 to 1.8 (comparison example 1), the performance of the catalyst decreases.
It is also found that a commercially available catalyst with high copper content (12.5% by weight), probably prepared with the co-precipitation method, in which the X/Y ratio is 3, does not have satisfactory selectivity.
In the field of catalysts for oxychlorination of ethylene to 1,2-DCE with a high copper content, the need is felt for catalysts that yield a satisfactory performance even when the X/Y ratio is high. This because a sufficiently high x/Y ratio ensures a long life of the catalyst.